Molecular sieve SSZ-27

ABSTRACT

A new crystalline molecular sieve designated SSZ-27 is disclosed. SSZ-27 is synthesized using a hexamethyl [4.3.3.0] propellane-8,11-diammonium cation as a structure directing agent.

TECHNICAL FIELD

This disclosure relates to a new crystalline molecular sieve designatedSSZ-27, a method for preparing SSZ-27, and uses for SSZ-27.

BACKGROUND

Molecular sieves are a class of important materials used in the chemicalindustry for processes such as gas stream purification and hydrocarbonconversion processes. Molecular sieves are porous solids havinginterconnected pores of different sizes. Molecular sieves typically havea one-, two- or three-dimensional crystalline pore structure havingpores of one or more molecular dimensions that selectively adsorbmolecules that can enter the pores, and exclude those molecules that aretoo large. The pore size, pore shape, interstitial spacing or channels,composition, crystal morphology and structure are a few characteristicsof molecular sieves that determine their use in various hydrocarbonadsorption and conversion processes.

For the petroleum and petrochemical industries, the most commerciallyuseful molecular sieves are known as zeolites. A zeolite is analuminosilicate having an open framework structure formed fromcorner-sharing the oxygen atoms of [SiO₄] and [AlO₄] tetrahedra. Mobileextra framework cations reside in the pores for balancing charges alongthe zeolite framework. These charges are a result of substitution of atetrahedral framework cation (e.g., Si⁴⁺) with a trivalent orpentavalent cation. Extra framework cations counter-balance thesecharges preserving the electroneutrality of the framework, and thesecations are exchangeable with other cations and/or protons.

Synthetic molecular sieves, particularly zeolites, are typicallysynthesized by mixing sources of alumina and silica in an aqueous media,often in the presence of an organic structure directing agent ortemplating agent. The structure of the molecular sieve formed isdetermined in part by the solubility of the various sources, thesilica-to-alumina ratio, the nature of the cation, the synthesisconditions (temperature, pressure, mixing agitation), the order ofaddition, the type of structure directing agent, and the like.

Although many different crystalline molecular sieves have beendiscovered, there is a continuing need for new molecular sieves withdesirable properties for gas separation and drying, hydrocarbon andchemical conversions, and other applications. New molecular sieves maycontain novel internal pore architectures, providing enhancedselectivities in these processes.

SUMMARY

The present disclosure is directed to a new family of molecular sieveswith unique properties, referred to herein as “molecular sieve SSZ-27”or simply “SSZ-27.”

In one aspect, there is provided a crystalline molecular sieve having,in its calcined form, the X-ray diffraction lines of Table 3.

In another aspect, there is provided a method of preparing a crystallinemolecular sieve by contacting under crystallization conditions (1) atleast one source of silicon; (2) at least one source of aluminum; (3) atleast one source of an element selected from Groups 1 and 2 of thePeriodic Table; (4) hydroxide ions; and (5) hexamethyl [4.3.3.0]propellane-8,11-diammonium cations.

In yet another aspect, there is provided a process for preparing acrystalline molecular sieve having, in its as-synthesized form, theX-ray diffraction lines of Table 2, by: (a) preparing a reaction mixturecontaining (1) at least one source of silicon; (2) at least one sourceof aluminum; (3) at least one source of an element selected from Groups1 and 2 of the Periodic Table; (4) hydroxide ions; (5) hexamethyl[4.3.3.0] propellane-8,11-diammonium cations; and (6) water; and (b)subjecting the reaction mixture to crystallization conditions sufficientto form crystals of the molecular sieve.

The present disclosure also provides a novel molecular sieve designatedSSZ-27 having, in its as-synthesized, anhydrous form, a composition, interms of mole ratios, in the range: Al₂O₃: 20-80 SiO₂ or morepreferably: Al₂O₃: 20-35 SiO₂.

DETAILED DESCRIPTION

Introduction

In preparing SSZ-27, a hexamethyl [4.3.3.0] propellane-8,11-diammoniumcation is used as a structure directing agent (“SDA”), also known as acrystallization template. The SDA useful for making SSZ-27 has thefollowing structure (1):

including syn, syn; syn, anti; and anti, anti orientations of theammonium groups.

The SDA dication is associated with anions which may be any anion thatis not detrimental to the formation of SSZ-27. Representative anionsinclude elements from Group 17 of the Periodic Table (e.g., fluoride,chloride, bromide and iodide), hydroxide, sulfate, tetrafluoroborate,acetate, carboxylate, and the like. As used herein, the numbering schemefor the Periodic Table Groups is as disclosed in Chem. Eng. News, 63(5),27 (1985).

Reaction Mixture

In general, SSZ-27 is prepared by: (a) preparing a reaction mixturecontaining (1) at least one source of silicon; (2) at least one sourceof aluminum; (3) at least one source of an element selected from Groups1 and 2 of the Periodic Table; (4) hydroxide ions; (5) hexamethyl[4.3.3.0] propellane-8,11-diammonium cations; and (6) water; and (b)subjecting the reaction mixture to crystallization conditions sufficientto form crystals of the molecular sieve.

The composition of the reaction mixture from which the molecular sieveis formed, in terms of mole ratios, is identified in Table 1 below

TABLE 1 Components Broad Exemplary SiO₂/Al₂O₃ 20 to 80 20 to 35 M/SiO₂0.05 to 0.50 0.15 to 0.30 Q/SiO₂ 0.10 to 0.40 0.10 to 0.30 OH/SiO₂ 0.25to 0.60 0.25 to 0.50 H₂O/SiO₂ 10 to 60 20 to 50wherein Q is a hexamethyl [4.3.3.0] propellane-8,11-diammonium cationand M is selected from the group consisting of elements from Groups 1and 2 of the Periodic Table.

Sources useful herein for silicon include fumed silica, precipitatedsilicates, silica hydrogel, silicic acid, colloidal silica, tetra-alkylorthosilicates (e.g., tetraethyl orthosilicate), and silica hydroxides.

Sources useful for aluminum include oxides, hydroxides, acetates,oxalates, ammonium salts and sulfates of aluminum. Typical sources ofaluminum oxide include aluminates, alumina, and aluminum compounds suchas aluminum chloride, aluminum sulfate, aluminum hydroxide, kaolinclays, and other zeolites. An example of the source of aluminum oxide iszeolite Y.

As described herein above, for each embodiment described herein, thereaction mixture can be formed using at least one source of an elementselected from Groups 1 and 2 of the Periodic Table (referred to hereinas M). In one sub-embodiment, the reaction mixture is formed using asource of an element from Group 1 of the Periodic Table. In anothersub-embodiment, the reaction mixture is formed using a source of sodium(Na). Any M-containing compound which is not detrimental to thecrystallization process is suitable. Sources for such Groups 1 and 2elements include oxides, hydroxides, nitrates, sulfates, halides,acetates, oxalates, and citrates thereof.

For each embodiment described herein, the molecular sieve reactionmixture can be supplied by more than one source. Also, two or morereaction components can be provided by one source.

The reaction mixture can be prepared either batch wise or continuously.Crystal size, morphology and crystallization time of the molecular sievedescribed herein can vary with the nature of the reaction mixture andthe crystallization conditions.

Crystallization and Post-Synthesis Treatment

In practice, the molecular sieve is prepared by: (a) preparing areaction mixture as described herein above; and (b) subjecting thereaction mixture to crystallization conditions sufficient to formcrystals of the molecular sieve (see, e.g., H. Robson, VerifiedSyntheses of Zeolitic Materials, Second Revised Edition, Elsevier,2001).

The reaction mixture is maintained at an elevated temperature until thecrystals of the molecular sieve are formed. The hydrothermalcrystallization is usually conducted under pressure, and usually in anautoclave so that the reaction mixture is subject to autogenouspressure, at a temperature between 150° C. and 180° C., e.g., from 170°C. to 175° C.

The reaction mixture can be subjected to mild stirring or agitationduring the crystallization step. It will be understood by one skilled inthe art that the molecular sieves described herein can containimpurities, such as amorphous materials, unit cells having frameworktopologies which do not coincide with the molecular sieve, and/or otherimpurities (e.g., organic hydrocarbons).

During the hydrothermal crystallization step, the molecular sievecrystals can be allowed to nucleate spontaneously from the reactionmixture. The use of crystals of the molecular sieve as seed material canbe advantageous in decreasing the time necessary for completecrystallization to occur. In addition, seeding can lead to an increasedpurity of the product obtained by promoting the nucleation and/orformation of the molecular sieve over any undesired phases. When used asseeds, seed crystals are added in an amount between 1% and 10% of theweight of the source for silicon used in the reaction mixture.

Once the molecular sieve crystals have formed, the solid product isseparated from the reaction mixture by standard mechanical separationtechniques such as filtration. The crystals are water-washed and thendried to obtain the as-synthesized molecular sieve crystals. The dryingstep can be performed at atmospheric pressure or under vacuum.

The molecular sieve can be used as-synthesized, but typically will bethermally treated (calcined). The term “as-synthesized” refers to themolecular sieve in its form after crystallization, prior to removal ofthe SDA cation. The SDA can be removed by thermal treatment (e.g.,calcination), preferably in an oxidative atmosphere (e.g., air, gas withan oxygen partial pressure of greater than 0 kPa) at a temperaturereadily determinable by one skilled in the art sufficient to remove theSDA from the molecular sieve. The SDA can also be removed by photolysistechniques (e.g., exposing the SDA-containing molecular sieve product tolight or electromagnetic radiation that has a wavelength shorter thanvisible light under conditions sufficient to selectively remove theorganic compound from the molecular sieve) as described in U.S. Pat. No.6,960,327.

The molecular sieve can subsequently be calcined in steam, air or inertgas at temperatures ranging from 200° C. to 800° C. for periods of timeranging from 1 to 48 hours, or more. Usually, it is desirable to removethe extra-framework cation (e.g., Na⁺) by ion exchange and replace itwith hydrogen, ammonium, or any desired metal-ion. Particularlypreferred cations are those which tailor the catalytic activity forcertain hydrocarbon conversion reactions. These include hydrogen, rareearth metals and metals of Groups 2 to 15 of the Periodic Table of theElements.

Where the molecular sieve formed is an intermediate material, the targetmolecular sieve can be achieved using post-synthesis techniques such asheteroatom lattice substitution techniques in order to achieve a higherSiO₂/Al₂O₃ ratio. The target molecular sieve can also be achieved byremoving heteroatoms from the lattice by known techniques such as acidleaching.

The molecular sieve made from the process disclosed herein can be formedinto a wide variety of physical shapes. Generally speaking, themolecular sieve can be in the form of a powder, a granule, or a moldedproduct, such as extrudate having a particle size sufficient to passthrough a 2-mesh (Tyler) screen and be retained on a 400-mesh (Tyler)screen. In cases where the catalyst is molded, such as by extrusion withan organic binder, the molecular sieve can be extruded before drying ordried (or partially dried) and then extruded.

The molecular sieve can be composited with other materials resistant tothe temperatures and other conditions employed in organic conversionprocesses. Such matrix materials include active and inactive materialsand synthetic or naturally occurring zeolites as well as inorganicmaterials such as clays, silica and metal oxides. Examples of suchmaterials and the manner in which they can be used are disclosed in U.S.Pat. Nos. 4,910,006 and 5,316,753.

Characterization of the Molecular Sieve

SSZ-27 has, in its as-synthesized, anhydrous form, a composition, interms of mole ratios, in the range: Al₂O₃: 20-80 SiO₂ or morepreferably: Al₂O₃: 20-35 SiO₂.

Molecular sieves synthesized by the process disclosed herein arecharacterized by their X-ray diffraction (XRD) pattern. The product ofthe synthesis reaction is a crystalline molecular sieve containingwithin its pore structure hexamethyl [4.3.3.0]propellane-8,11-diammonium cations. The resultant as-synthesizedmaterial has an X-ray diffraction pattern which is distinguished fromthe patterns of other known as-synthesized or thermally treatedcrystalline materials by the lines listed in Table 2 below.

TABLE 2 Characteristic Peaks for As-Synthesized SSZ-27 2-Theta^((a))d-Spacing, nm Relative Intensity^((b)) 7.57 1.167 W 8.62 1.025 W 9.350.946 M 9.83 0.900 W 13.55 0.653 W 14.80 0.598 W 15.27 0.580 W 16.250.545 W 17.72 0.500 W 19.76 0.449 M 20.50 0.433 W 21.08 0.421 S 21.300.417 M 21.93 0.405 S 22.95 0.387 VS ^((a))±0.20 ^((b))The powder XRDpatterns provided are based on a relative intensity scale in which thestrongest line in the powder X-ray pattern is assigned a value of 100: W= weak (>0 to ≦20); M = medium (>20 to ≦40); S = strong (>40 to ≦60); VS= very strong (>60 to ≦100).

The X-ray diffraction pattern of the calcined form of SSZ-27 includesthe lines listed in Table 3 below:

TABLE 3 Characteristic Peaks for Calcined SSZ-27 2-Theta^((a))d-Spacing, nm Relative Intensity^((b)) 7.50 1.177 W 8.65 1.021 W 9.470.933 VS 9.94 0.889 M 13.47 0.657 M 14.86 0.596 M 16.07 0.551 W 16.370.541 W 17.92 0.495 W 19.92 0.445 W 20.66 0.430 W 21.14 0.420 W 21.340.416 W 22.07 0.402 M 23.17 0.384 M ^((a))±0.20 ^((b))The powder XRDpatterns provided are based on a relative intensity scale in which thestrongest line in the powder X-ray pattern is assigned a value of 100: W= weak (>0 to ≦20); M = medium (>20 to ≦40); S = strong (>40 to ≦60); VS= very strong (>60 to ≦100).

The powder X-ray diffraction patterns presented herein were collected bystandard techniques. The radiation was CuK_(α) radiation. The peakheights and the positions, as a function of 2θ where θ is the Braggangle, were read from the relative intensities of the peaks (adjustingfor background), and d, the interplanar spacing corresponding to therecorded lines, can be calculated.

Minor variations in the diffraction pattern can result from variationsin the mole ratios of the framework species of the particular sample dueto changes in lattice constants. In addition, sufficiently smallcrystals will affect the shape and intensity of peaks, leading tosignificant peak broadening. Minor variations in the diffraction patterncan also result from variations in the organic compound used in thepreparation. Calcination can also cause minor shifts in the XRD pattern.Notwithstanding these minor perturbations, the basic crystal latticestructure remains unchanged.

Processes Using SSZ-27

SSZ-27 can be useful as an adsorbent for gas separations. SSZ-27 canalso be used as a catalyst for converting oxygenates (e.g., methanol) toolefins and for making small amines. SSZ-27 can be used to reduce oxidesof nitrogen in a gas streams, such as automobile exhaust. SSZ-27 canalso be used to as a cold start hydrocarbon trap in combustion enginepollution control systems. SSZ-27 is particularly useful for trapping C₃fragments.

EXAMPLES

The following illustrative examples are intended to be non-limiting.

Example 1 Synthesis of SSZ-27

1 mmole of the SDA in the OH form, in 2.5 g of water, was added into aTeflon liner for a 23 mL Parr reactor. Next, 2 g of 1 N NaOH solutionwas added, followed by 1 g of water, and Na—Y zeolite (CBV100, ZeolystInternational, SiO₂/Al₂O₃ mole ratio=5.1) as the aluminum source.Finally, 0.60 g of CAB-O-SIL® M5 fumed silica (Cabot Corporation) wasadded. The liner was capped and placed within a Parr steel autoclavereactor. The autoclave was then fixed in a rotating spit (43 rpm) withinan oven heated at 170° C. for 7-10 days. The solid products wererecovered, washed thoroughly with deionized water and dried.

The resulting product was analyzed by powder XRD and indicated that thematerial is unique.

Example 2 Seeded Synthesis of SSZ-27

Example 1 was repeated with the exception that as-synthesized zeolitefrom Example 1 was added to the reaction mixture as seed material (2% ofthe weight of the silicon source). The crystallization was complete in6-7 days, as confirmed by powder XRD.

Example 3 Calcination of SSZ-27

The as-synthesized product of Example 1 was calcined inside a mufflefurnace under a flow of air heated to 595° C. at a rate of 1° C./minuteand held at 595° C. for 5 hours, cooled and then analyzed by powder XRD.The powder XRD pattern of the resulting product indicated that thematerial remains stable after calcination to remove the organic SDA.

Example 4 Ammonium-Ion Exchange of SSZ-27

The calcined material from Example 3 (Na-SSZ-27) was treated with 10 mL(per g of zeolite) of a 1 N ammonium nitrate solution at 90° C. for 2hours. The solution was cooled, decanted off and the same processrepeated.

The product (NH₄-SSZ-27) after drying was subjected to a microporevolume analysis using N₂ as adsorbate and via the BET method. Thezeolite exhibited a micropore volume of 0.11 cm/g and indicates thatSSZ-27 has microporous character.

Example 5 Methanol Conversion

The product made in Example 4 was pelletized at 5 kpsi, crushed andmeshed to 20-40. 0.25 g of catalyst (diluted 4:1 v/v with alundum) wascentered in a stainless steel downflow reactor in a split tube furnace.The catalyst was pre-heated in-situ under flowing nitrogen at 400° C. Afeed of 10% methanol in nitrogen was introduced into the reactor at arate of 1.0 h⁻¹ WHSV.

Reaction data was collected using a plug flow and an Agilent on-line gaschromatograph with an FID detector. Reaction products were analyzed at 1hour and 2 hours on an HP-PLOT Q column. The results are summarized inTable 4.

TABLE 4 Product 1 Hour Data 2 Hour Data Methane 9.0 4.5 Ethane 13.3 2.2Ethylene 13.5 33.8 Propane 3.3 11.9 Propylene 4.8 28.3 SummedButanes/Butenes 11.5 13.5 Summed Pentanes/Pentenes 25.0 5.5

The products shown in Table 4 are consistent with those for a small porezeolite in terms of product shape-selectivity in the reaction ofmethanol being catalytically converted to olefins of mostly C₂-C₄ size.

As used herein, the term “comprising” means including elements or stepsthat are identified following that term, but any such elements or stepsare not exhaustive, and an embodiment can include other elements orsteps.

Unless otherwise specified, the recitation of a genus of elements,materials or other components, from which an individual component ormixture of components can be selected, is intended to include allpossible sub-generic combinations of the listed components and mixturesthereof.

All documents cited in this application are herein incorporated byreference in their entirety to the extent such disclosure is notinconsistent with this text.

The invention claimed is:
 1. A crystalline molecular sieve having, inits calcined form, an X-ray diffraction pattern including the lineslisted in the following table: 2-Theta d-Spacing, nm Relative Intensity 7.50 ± 0.20 1.177 W  8.65 ± 0.20 1.021 W  9.47 ± 0.20 0.933 VS  9.94 ±0.20 0.889 M 13.47 ± 0.20 0.657 M 14.86 ± 0.20 0.596 M 16.07 ± 0.200.551 W 16.37 ± 0.20 0.541 W 17.92 ± 0.20 0.495 W 19.92 ± 0.20 0.445 W20.66 ± 0.20 0.430 W 21.14 ± 0.20 0.420 W 21.34 ± 0.20 0.416 W 22.07 ±0.20 0.402 M 23.17 ± 0.20 0.384 M.


2. The molecular sieve of claim 1, wherein the molecular sieve has aSiO₂/Al₂O₃ mole ratio of from 20 to
 80. 3. The molecular sieve of claim1, wherein the molecular sieve has a SiO₂/Al₂O₃ mole ratio of from 20 to35.
 4. A crystalline molecular sieve having, in its as-synthesized form,an X-ray diffraction pattern including the lines in the following table:2-Theta d-Spacing, nm Relative Intensity  7.57 ± 0.20 1.167 W  8.62 ±0.20 1.025 W  9.35 ± 0.20 0.946 M  9.83 ± 0.20 0.900 W 13.55 ± 0.200.653 W 14.80 ± 0.20 0.598 W 15.27 ± 0.20 0.580 W 16.25 ± 0.20 0.545 W17.72 ± 0.20 0.500 W 19.76 ± 0.20 0.449 M 20.50 ± 0.20 0.433 W 21.08 ±0.20 0.421 S 21.30 ± 0.20 0.417 M 21.93 ± 0.20 0.405 S 22.95 ± 0.200.387 VS.


5. The molecular sieve of claim 4, wherein the molecular sieve compriseshexamethyl [4.3.3.0] propellane-8,11-diammonium cations within its porestructure.
 6. The molecular sieve of claim 4, wherein the molecularsieve has a SiO₂/Al₂O₃ mole ratio of 20 to
 80. 7. The molecular sieve ofclaim 4, wherein the molecular sieve has a SiO₂/Al₂O₃ mole ratio of from20 to 35.